CN107155324A - Amorphous mesoporous aluminas of distribution of pores with optimization and preparation method thereof - Google Patents
Amorphous mesoporous aluminas of distribution of pores with optimization and preparation method thereof Download PDFInfo
- Publication number
- CN107155324A CN107155324A CN201580043496.3A CN201580043496A CN107155324A CN 107155324 A CN107155324 A CN 107155324A CN 201580043496 A CN201580043496 A CN 201580043496A CN 107155324 A CN107155324 A CN 107155324A
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- China
- Prior art keywords
- precursor
- minutes
- aluminum oxide
- progress
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011148 porous material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 24
- 238000009826 distribution Methods 0.000 title description 18
- 238000005457 optimization Methods 0.000 title description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000002243 precursor Substances 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- 239000004411 aluminium Substances 0.000 claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 31
- 238000002347 injection Methods 0.000 claims abstract description 26
- 239000007924 injection Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012429 reaction media Substances 0.000 claims abstract description 13
- 239000012431 aqueous reaction media Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 65
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 40
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 39
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 abstract description 13
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 40
- 238000001556 precipitation Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 8
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 7
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000002459 porosimetry Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 150000001399 aluminium compounds Chemical group 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
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- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
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- C01P2006/14—Pore volume
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- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
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- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Abstract
The present invention relates to 16 nanometers or the bigger intermediate value median pore diameter for pressing the stereometer by mercury injection apparatus measure, 0.5 ml/g or the bigger mesopore volume measured by mercury injection apparatus, and the total pore size volume measured by mercury injection method more than 0.75 ml/g amorphous mesoporous aluminas.The invention further relates to prepare the method for the aluminum oxide, including：a）First step for precipitating at least one alkaline precursor and at least one acidic precursor, wherein at least one of the alkalescence or acidic precursor include aluminium, the pH of the aqueous reaction medium is 8.5 to 10.5, temperature is 20 DEG C to 90 DEG C and carried out 2 minutes to 30 minutes that the state of progress of first step is 5% to 13%；b）The step of heating suspension；c）The second step precipitated by adding at least one alkaline precursor and at least one acidic precursor into suspension, wherein at least one of the alkalescence or acidic precursor include aluminium, the pH of the reaction medium is 8.5 to 10.5, temperature is 40 DEG C to 90 DEG C and carried out 2 minutes to 50 minutes that the state of progress of second step is 87% to 95%；d）Filtration step；e）Drying steps；f）Forming step；g）Heat treatment step.
Description
Invention field
It is described the present invention relates to the amorphous mesoporous aluminas that shaping is prepared since with low dispersed alumina gel
Alumina gel is obtained by the method including two steps for precipitating at least one aluminum precursor, in the first gel precipitation
In step process relative to gel set-up procedure at the end of the aluminum oxide total amount that is formed produce the aluminum oxide of controlled quatity.
Especially, the present invention relates to the amorphous mesoporous aluminas being distributed with specific pore.It is special due to its related property
It is not that in terms of distribution of pores, aluminum oxide of the invention may be used as the carrier of the catalyst in all refining process, and may be used also
For use as adsorbent.
Prior art
It is this area that alumina gel is prepared by the precipitation in a settling step or in two settling steps
Known to technical staff.
For example, patent US 6 589 908 describes the method for preparing aluminum oxide, the aluminum oxide is characterised by not depositing
In macropore, 5% hole for being more than 35 nanometers by diameter that is less than of total pore size volume is constituted, the high pore-body more than 0.8 ml/g
Product, and bimodal pore distribution, two of which pattern is separated by 1 to 20 nanometer, and main aperture gap pattern is more than mean pore sizes.
In this respect, the pattern uses the precipitated alumina precursors under the temperature well controlled, pH and flow condition
Two steps.First step is operated at 25 DEG C to 60 DEG C of temperature and 3 to 10 pH.Suspension is then heated to 50 DEG C extremely
90 DEG C of temperature.Reactant is added in the suspension again, is then washed, dried, shaped and calcined and urged with being formed
Agent carrier.
The dispersed information on the alumina gel is not provided, the progress shape on first step is not provided yet
Regioselective any information of state, the state of progress is 14% to 34% in the presented embodiments.
In addition, patent US 7 790 652 is described prepares the aluminum oxide with very special distribution of pores by precipitating
Carrier；The carrier can be used as catalyst carrier in the hydroconversion process of heavy hydrocarbon charge.
The alumina support is prepared according to following methods, methods described is included by mixing the first alkaline water in a controlled manner
Solution and the first acidic aqueous solution（The acid and/or alkaline solution includes aluminium compound）To form the of aluminium oxid-dispersion
One step.The acidity and alkaline solution are to cause dispersions obtained pH to be mixed as 8 to 11 ratio.The acidity and alkaline solution
Also with available for the amount mixing for producing the dispersion containing the desired amount of aluminum oxide；Especially, the first step can be used for obtaining
Relative to 25 to 35 weight % of the aluminum oxide total amount formed at the end of two settling steps aluminum oxide.The first step exists
Operated at a temperature of 20 to 40 DEG C.When forming the desired amount of aluminum oxide, the temperature of the suspension is brought up to 45 to 70 DEG C
Temperature, then makes the suspension of heating by making the suspension be contacted with the second alkaline aqueous solution and the second acidic aqueous solution
Undergo the second settling step, at least one of described two solution or both include aluminium compound.In addition, the acid for passing through addition
Property and alkaline solution ratio by pH adjust to 8 to 10.5, treat that the surplus of the aluminum oxide formed in the second step passes through
Second acidity of addition is provided with the amount of alkaline solution.The second step is operated at a temperature of 20 to 40 DEG C.It is consequently formed
Alumina gel include at least 95% boehmite.The dispersiveness of thus obtained alumina gel is not mentioned.Then use
Method known to those skilled in the art filters the alumina gel, washs and optionally drying is to produce alumina powder, with
The alumina powder is shaped using method known to those skilled in the art afterwards, and then calcines to produce final oxidation
Alumina supporter.
First settling step of patent US 7 790 652 preparation method is limited to 25 to 35 weight % aluminum oxide production
Amount；The higher yield of aluminum oxide does not allow to carry out optimum filtration to the gel of acquisition at the end of first step.The material of acquisition
Be based on high-specific surface area, 0.75 ml/g or higher of total pore size volume, 10 to 14 nanometers of mean pore sizes oxidation
The carrier of aluminium.The pore volume is made up of less than 5% the hole with the intermediate value median pore diameter more than 21 nanometers.
Surprisingly, applicants have discovered the oxygen that shaping is prepared since with low dispersed specific aluminum oxide
Change the new method of aluminium, the aluminum oxide is prepared according to the method for two steps including being used to precipitate at least one aluminum precursor,
The aluminum oxide total amount formed at the end of wherein being formed in the first settling step relative to the gel process for preparing it is only controlled
And finite quantity, 5 weight % to 13 weight % aluminum oxide.It has been discovered by the applicants that can make described gel shaped and calcine to obtain
There must be the amorphous of high pore volume, high-specific surface area, specific unimodal middle pore size distribution and very high intermediate value median pore diameter
Mesoporous aluminas.
It is an object of the present invention to provide the amorphous mesopore with specific unimodal middle pore size distribution and high average pore size
Aluminum oxide.
It is a further object of the present invention to provide by making with low dispersiveness（Typically smaller than 15% and specifically for less than 10%）
And the method that the alumina gel with 1 to 35 nanometer of crystallite dimension shapes to prepare the aluminum oxide.
Goal of the invention
It is an object of the invention to provide the amorphous mesopore for high aperture and in mesopore domain being unimodal specific pore distribution
Aluminum oxide.
An advantage of the invention that it provides aluminum oxide, the porosity of the aluminum oxide is characterised by 10 to 30
Nanometer, particularly with 16 nanometers or it is bigger, preferably 18 nanometers or bigger, highly preferred 20 nanometers or bigger and even more preferably from 21
To 23 nanometers（Including limit value）Intermediate value median pore diameter hole very high contribution.
The porosity illustrates the weight spread in the catalytic reaction process using these materials for pending molecule
Want advantage.
Present invention also offers the method for preparing the aluminum oxide, methods described includes at least following steps：
a）It is at least one selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide for being precipitated in aqueous reaction medium
Alkaline precursor and it is at least one selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, the acidic precursor of hydrochloric acid and nitric acid first
Step, wherein at least one of the alkalescence or acidic precursor include aluminium, select acidity and alkalescence precursor relative discharge with
Just in the pH for the reaction medium for obtaining 8.5 to 10.5, and the acidity containing aluminium and alkaline precursor are adjusted（It is one or more）Stream
Amount is with the state of progress for the first step for obtaining 5% to 13%, and the state of progress is defined as in the first settling step mistake
Formed in journey with Al2O3As step c of the aluminum oxide relative to the preparation method of gauge）At the end of the aluminum oxide total amount that is formed
Ratio, the step is operated at a temperature of 20 DEG C to 90 DEG C and carried out 2 minutes to 30 minutes；
b）The step of suspension is heated to 40 DEG C to 90 DEG C of temperature 7 minutes to 45 minutes；
c）By adding at least one alkali selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide into the suspension
Property precursor and at least one acidic precursor selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid precipitate heating
Step b）At the end of the second step of suspension that obtains, wherein at least one of alkalescence or acidic precursor includes aluminium, choosing
The relative discharge of the acidity and alkaline precursor is selected so as in the pH for the reaction medium for obtaining 8.5 to 10.5, and adjusts and contains aluminium
The flow of acid and alkaline precursor is to obtain the state of progress of 87% to 95% second step, and the state of progress is defined as
Formed during second settling step with Al2O3As step c of the aluminum oxide relative to the preparation method of gauge）At the end of
The ratio of the aluminum oxide total amount of formation, the step is operated at a temperature of 40 DEG C to 90 DEG C and carried out 2 minutes to 50 minutes；
d）Filter the second settling step c）At the end of the suspension that obtains to obtain alumina gel the step of；
e）Drying steps d）The step of alumina gel of middle acquisition is to obtain powder, the drying steps preferably by
Dried 8 hours to 15 hours at a temperature of 20 DEG C to 200 DEG C or by spray drying or by well known by persons skilled in the art
Any other method is operated；
f）Make step e）At the end of the powder forming that obtains to obtain green material the step of；
g）In the case of presence or absence of the air stream of the water containing most 60 volume %, in 500 DEG C to 1000 DEG C of temperature
Lower heat treatment step f）At the end of obtain green material the step of.
It is one advantage of the present invention that there is provided preparing the new of amorphous mesoporous aluminas since specific alumina gel
Method, the specific alumina gel is prepared using the method for two steps including being used to precipitate at least one aluminum precursor,
Only 5% relative to the aluminum oxide total amount formed at the end of the gel process for preparing is wherein formed in the first settling step
To 13% aluminum oxide, the specific alumina gel have advantageously below 15%, preferably 6% to 13% and highly preferred 6% to
10% dispersiveness.The alumina preparation method of the present invention, which can be used for obtaining, has specific pore distribution, particularly high pore volume
With high intermediate value median pore diameter（Particularly 16 nanometers or bigger）Amorphous mesoporous aluminas.
Term
In whole this paper remainder, dispersiveness is defined as being not able to by centrifuging 3 points under 3600 G in PA tube
Clock carrys out the weight of scattered solid or peptized alumina gel.
The aluminum oxide of the present invention also there is specific pore to be distributed, wherein macropore and mesopore volume are measured by mercury injection method, and
Micro pore volume is measured by nitrogen adsorption method.
Term " macropore " refers to the hole with the opening more than 50 nanometers.
Term " mesopore " refers to the hole with 2 nanometers to 50 nanometers of opening, including limit value.
Term " micropore " refers to the hole with the opening less than 2 nanometers.
In the disclosure below of the present invention, the distribution of pores measured by mercury injection method passes through according to standard ASTM D
Surface tension and 140 ° of contact angle of the 4284-83 mercury injection apparatus under the maximum pressure of 4000 bars, using 484 dynes per centimeters
To determine.Angle of wetting is taken equal to 140 °, it then follows works " Techniques de l'ing é nieur, trait é analyse
and caractérisation”[Engineering Techniques: Analysis and Characterization],
The 1050-5 pages, author：Suggestion in Jean Charpin and Bernard Rasneur.
Intermediate value median pore diameter（Dp, in units of nanometer）It is also defined as constituting in all holes that size is less than the diameter
The total mesopore volume measured by mercury injection method 50% when diameter.
Use Barrett-Joyner-Halenda（BJH）Model determines the distribution of pores measured by N2 adsorption.Should
Periodical " The of the BJH- models N2 adsorption-desorption isotherm description in E.P.Barrett, L.G.Joyner and P.P.Halenda
Journal of American Society ", 73,373, in (1951).
In the disclosure below of the present invention, term " specific surface area " refers to by according to based on periodical " The
Journal of American Society ", 60,309, the BRUNAUER-EMMETT-TELLER side described in (1938)
The BET specific surface area that the standard ASTM D 3663-78 of method N2 adsorption is determined.
By according to standard ASTM D 4284-83 mercury injection apparatus under the maximum pressure of 4000 bars, use 484 dynes/li
The surface tension and 140 ° of Contact-angle measurement macropore and the volume of mesopore of rice.
The value that thus mercury fill all intergranular pores is fixed on 0.2 MPa, and it is believed that more than the value, mercury penetrates into oxidation
In the hole of aluminium.
In order to obtain more preferable accuracy, hereinafter by ml/g in units of the value of total pore size volume that provides equivalent to
Sample is measured by ml/g in units of the value of cumulative volume that is measured by mercury injection apparatus subtract equivalent to 30 psi（About
0.2 MPa）Pressure under same sample is measured by ml/g in units of mercury volume value.
The macropore volume of aluminum oxide is hereby defined as the accumulation body of the mercury introduced under 0.2 MPa to 30 MPa pressure
Product, equivalent to the volume included in the hole that apparent diameter is more than 50 nanometers.
The mesopore volume of aluminum oxide be hereby defined as be the mercury introduced under 30 MPa to 400 MPa pressure accumulation
Volume, equivalent to the volume included in the hole that apparent diameter is 2 to 50 nanometers.
Micro pore volume is measured by nitrogen porosimetry." t " method of use（Lippens-De Boer methods, 1965）Carry out
The quantitative analysis of microporosity, its works equivalent to such as F. Rouqu é rol, J. Rouqu é rol and K. Sing
“Adsorption by powders and porous solids. Principles, methodology and
Applications ", Academic Press, the conversion of the starting adsorption isotherm described in 1999.
Summary of the invention
The present invention relates to the method for preparing amorphous mesoporous aluminas, methods described includes at least following steps：
a）It is at least one selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide for being precipitated in aqueous reaction medium
Alkaline precursor and it is at least one selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, the acidic precursor of hydrochloric acid and nitric acid first
Step, wherein at least one of the alkalescence or acidic precursor include aluminium, select acidity and alkalescence precursor relative discharge with
Just in the pH for the reaction medium for obtaining 8.5 to 10.5, and the acidity containing aluminium and alkaline precursor are adjusted（It is one or more）Stream
Amount is with the state of progress for the first step for obtaining 5% to 13%, and the state of progress is defined as in the first settling step mistake
Formed in journey with Al2O3When the aluminum oxide of gauge is relative in step c）At the end of the ratio of aluminum oxide total amount that is formed, the step
Suddenly operate and carry out 2 minutes to 30 minutes at a temperature of 20 to 90 DEG C；
b）The step of suspension is heated to 40 DEG C to 90 DEG C of temperature 7 minutes to 45 minutes；
c）By adding at least one alkali selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide into the suspension
Property precursor and at least one acidic precursor selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid precipitate heating
Step b）At the end of the second step of suspension that obtains, wherein at least one of alkalescence or acidic precursor includes aluminium, choosing
The relative discharge of the acidity and alkaline precursor is selected so as in the pH for the reaction medium for obtaining 8.5 to 10.5, and adjusts and contains aluminium
The flow of acid and alkaline precursor is to obtain the state of progress of 87% to 95% second step, and the state of progress is defined as
Formed during second settling step with Al2O3When the aluminum oxide of gauge is relative to the step c in preparation method）At the end of
The ratio of the aluminum oxide total amount of formation, the step is operated at a temperature of 40 DEG C to 90 DEG C and carried out 2 minutes to 50 minutes；
d）Filter the second settling step c）At the end of the suspension that obtains to obtain alumina gel the step of；
e）Drying steps d）The step of alumina gel of middle acquisition is to obtain powder；
f）Make step e）At the end of the powder forming that obtains to obtain green material the step of；
g）In the case of presence or absence of the air stream of the water containing most 60 volume %, in 500 DEG C to 1000 DEG C of temperature
Lower heat treatment step f）At the end of obtain green material the step of.
Preferably, the first settling step a）State of progress be 6% to 12%.
Highly preferable, the first settling step a）State of progress be 7% to 11%.
Preferably, the alkaline precursor is sodium aluminate.
Preferably, the acidic precursor is aluminum sulfate.
Preferably, in the first settling step, the aqueous reaction medium is water, and the step adds in the absence of organic
Plus carried out under agitation in the case of agent.
The invention further relates to 16 nanometers or the bigger intermediate value median pore diameter by volume determined by mercury injection apparatus,
0.5 ml/g or the bigger mesopore volume measured by mercury injection apparatus and being measured by mercury injection method more than 0.75 ml/g
The amorphous mesoporous aluminas of total pore size volume.
Preferably, macropore volume is less than 10% for total pore size volume, in fact it is highly preferred that be less than 5% for total pore size volume.
Preferably, the amorphous mesoporous aluminas does not have any micropore.
Preferably, the amorphous mesoporous aluminas have more than 18 nanometers, it is highly preferred be more than 20 nanometers by mercury injection apparatus
The intermediate value median pore diameter by volume determined.
The invention also relates to the amorphous mesoporous aluminas that the preparation method by the present invention is obtained.
Detailed description of the invention
The aluminum oxide of the present invention is with controlled mesopore rate, with good thermally and chemically stability, with concentration, uniform, list
Peak and the mesoporous aluminas of controlled intermediate pore size distribution.
The aluminum oxide advantageously has the specific surface area and pore volume, particularly mesopore volume of calibration.
Preferably, the mesoporous aluminas is free of micropore.
Preferably, the aluminum oxide, which advantageously has, is more than 75 m2/ g specific surface area.
Highly preferable, the specific surface area of the mesoporous aluminas is higher than 100 m2/g。
Even further preferably, the specific surface area of the mesoporous aluminas is more than 125 m2/g。
Mesopore volume is measured by mercury injection method, the mesopore volume is defined as being included in apparent diameter for 2 to 50 nanometers（Bag
Include limit value）Hole in volume.According to the present invention, the mesopore volume of the aluminum oxide is 0.5 ml/g or higher, highly excellent
Select 0.7 ml/g or higher, and even more preferably from 0.70 ml/g to 0.90 ml/g.
Preferably, aluminum oxide of the invention is the aluminum oxide of non-fine structure.
On the other hand, the present invention relates to the method for preparing the aluminum oxide.
According to the present invention, the preparation method includes the first step a for precipitating）, the step b for heating）, second
Settling step c）, the step d for filtering）, for dry step e）, the step f for shaping）With the step for heat treatment
Rapid g）.
The state of progress of each settling step is defined as being formed with Al during the described first or second settling step2O3
When at the end of the aluminum oxide of gauge is relative in two settling steps and at the end of being more typically in alumina gel preparation process and
Especially in the step c of preparation method of the invention）At the end of formed with Al2O3When the ratio of the aluminum oxide total amount of gauge.
Step a）：First precipitation
The step, which is included in aqueous reaction medium, makes at least one be selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and hydroxide
The alkaline precursor of potassium is contacted with least one acidic precursor selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid,
Wherein at least one of the alkalescence or acidic precursor include aluminium, select the acidity and the relative discharge of alkaline precursor obtaining
The pH of 8.5 to 10.5 reaction medium is obtained, and adjusts the acidity containing aluminium and alkaline precursor（It is one or more）Flow to obtain
The state of progress of 5% to 13% first step is obtained, the state of progress is defined as the shape during first settling step
Into with Al2O3When the aluminum oxide of gauge terminates relative at the end of the settling step, being more typically in alumina gel preparation process
When, the especially step c in the preparation method）At the end of the ratio of aluminum oxide total amount that is formed, the step is at 20 DEG C to 90
Operate and carry out 2 minutes to 30 minutes at a temperature of DEG C.
At least one alkaline precursor and at least one acidic precursor are mixed in aqueous reaction medium；It means that the acid
Property or at least one of alkaline precursor must include aluminium.Be also possible to the alkalescence and acidic precursor at least two include aluminium.
Alkaline precursor comprising aluminium is sodium aluminate and potassium aluminate.It is preferred that alkaline precursor be sodium aluminate.
Acidic precursor comprising aluminium is aluminum sulfate, aluminium chloride and aluminum nitrate.It is preferred that acidic precursor be aluminum sulfate.
Preferably, the aqueous reaction medium is water.
Preferably, the step a）Operate under agitation.
Preferably, the step a）Carried out in the case of in the absence of organic additive.
By the acidity and alkaline precursor（No matter whether they contain aluminium）In aqueous reaction medium with cause gained suspend
The pH of liquid mixes for 8.5 to 10.5 ratio（It is preferred that as a solution）.
According to the present invention, the acidic precursor of aluminum oxide and the alkaline precursor of aluminum oxide in the settling step can individually or
Used as mixture.
According to the present invention, the acidity and alkaline precursor are selected（No matter whether they contain aluminium）Relative discharge to obtain
PH in 8.5 to 10.5 reaction medium.
Under the alkalescence and acidic precursor are respectively the preferable case of sodium aluminate and aluminum sulfate wherein, the alkaline precursor pair
The weight ratio of the acidic precursor is advantageously 1.60 to 2.05.
For other alkalescence and acidic precursor, no matter whether they contain aluminium, and alkali/acid matter is set up by the figure that acid is neutralized by alkali
Amount ratio.Those skilled in the art can be readily available such figure.
Preferably, the settling step a）Carried out under 8.5 to 10.0 and highly preferred 8.7 to 9.9 pH.
Preferably, the first settling step a）At a temperature of 20 to 90 DEG C, preferably 20 to 70 DEG C and more preferably 30 to 50 DEG C
Carry out.
Preferably, the first settling step a）In 8 to 10.5, preferably 8 to 10.5, more preferably 8.5 to 10 and highly preferred 8.7
Carried out under to 9.9 pH.
Preferably, the first settling step a）Carry out 5 to 20 minutes, preferably 5 to 15 minutes.
According to the present invention, the first settling step a）State of progress be 5% to 13%, preferably 6% to 12% and preferably 7%
To 11%.State of progress is defined as being formed with Al during first settling step2O3When gauge aluminum oxide relative to
The step c of the preparation method）At the end of the ratio of aluminum oxide total amount that is formed.
According to final alumina concentration to be obtained, thus also the acidity containing aluminium is contained with alkaline precursor with resulting in
The amount for having the suspension of the desired amount of aluminum oxide is introduced.Especially, the step a）Available for acquisition relative to the preparation method
Step c）At the end of 5% to 13 weight % of the aluminum oxide total amount aluminum oxide that is formed.
Step b）：Heating
According to the present invention, the preparation method includes the first settling step a of heating）At the end of the step b of suspension that obtains）.
According to the present invention, before the second settling step is carried out, thermal precipitation step is carried out between two settling steps
a）At the end of obtain suspension the step of.
In the first settling step a）With the second settling step c）Between the heating stepses a that carries out）At the end of obtain
The step of suspension is at 40 DEG C to 90 DEG C, preferably 40 DEG C to 80 DEG C, preferably 40 DEG C to 70 DEG C and highly preferred 40 DEG C to 65
Operated at a temperature of DEG C.
The heating stepses are carried out 7 to 45 minutes, preferably 7 to 35 minutes.
The heating stepses are carried out advantageously with any heating means well known by persons skilled in the art.
Step c）：Second precipitation
According to the present invention, the preparation method includes being used to precipitate heating stepses b）At the end of obtain the of the suspension of heating
Two steps, the second step is at least one selected from sodium aluminate, potassium aluminate, ammonia, hydroxide by being added into the suspension
The alkaline precursor and at least one acid selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid of sodium and potassium hydroxide
Property precursor operate, wherein at least one of alkalescence or acidic precursor includes aluminium, selects the phase of acidity and alkalescence precursor
To flow so as in the pH for the reaction medium for obtaining 8.5 to 10.5, and adjust the flow of the acidity containing aluminium and alkaline precursor with
The state of progress of 87% to 95% second step is obtained, the state of progress is defined as during second settling step
Formed with Al2O3As step c of the aluminum oxide relative to the preparation method of gauge）At the end of the ratio of aluminum oxide total amount that is formed,
The step is operated at a temperature of 40 DEG C to 90 DEG C and carried out 2 minutes to 50 minutes.
The alkalescence and acidic precursor（It is one or more）Added in form of an aqueous solutions in the second step.
With similar to the first settling step a）Mode, at least one alkaline precursor and extremely is added into the suspension of heating
A kind of few acidic precursor requires that at least one of the alkalescence or acidic precursor include aluminium.It is also possible to the alkalescence and acidic precursor
At least two include aluminium.
Alkaline precursor comprising aluminium is sodium aluminate and potassium aluminate.It is preferred that alkaline precursor be sodium aluminate.
Acidic precursor comprising aluminium is aluminum sulfate, aluminium chloride and aluminum nitrate.It is preferred that acidic precursor be aluminum sulfate.
Preferably, second settling step is operated under agitation.
Preferably, the second step is carried out in the case of in the absence of organic additive.
By the acidity and alkaline precursor（No matter whether they contain aluminium）To cause the pH of gained suspension as 8.5 to 10.5
Ratio be mixed into suspension（It is preferred that as a solution）.
With similar to settling step a）Mode, select the acidity and alkaline precursor（No matter whether they contain aluminium）Phase
To flow to obtain 8.5 to 10.5, preferably 8.5 to 10, even more preferably from 8.7 to 9.9 reaction medium pH.
Under the alkalescence and acidic precursor are respectively the preferable case of sodium aluminate and aluminum sulfate wherein, the alkaline precursor pair
The weight ratio of the acidic precursor is advantageously 1.60 to 2.05.
For other alkalescence and acidic precursor, no matter whether they contain aluminium, and alkali/acid matter is set up by the figure that acid is neutralized by alkali
Amount ratio.Those skilled in the art can be readily available such figure.
Preferably, second settling step is carried out under 8.5 to 10.0, preferably 8.7 to 9.9 pH.
According to final alumina concentration to be obtained, also by the aluminum precursor can produce containing the desired amount of aluminum oxide
Suspension amount mixing.Especially, second settling step can be used for obtaining shape at the end of relative to two settling steps
Into aluminum oxide total amount 87 weight % to 95 weight % aluminum oxide.
With similar to settling step a）Mode, acidity of the regulation containing aluminium with the flow of alkaline precursor with obtain 87% to
95%th, preferably 88% to 94%, the state of progress of highly preferred 89% to 93% second step, the state of progress is defined as in institute
State and formed with Al during the second settling step2O3As step c of the aluminum oxide relative to the preparation method of gauge）At the end of shape
Into aluminum oxide total amount ratio.
Thus, depending on settling step at the end of desired alumina concentration（It is preferred that 20 to 100 g/l）, calculate by
The amount for the aluminium that the acidity and/or alkaline precursor are provided, and according to the concentration containing aluminum precursor of the addition, be added to reaction medium
In water and state of progress needed for each settling step adjust the flow of the precursor.
With similar to settling step a）Mode, the flow of the acid and/or alkaline precursor containing aluminium depends on used anti-
The size of device is answered, and thus depending on the water being added in reaction medium.
By way of example, if obtaining 1 liter using 3 liters of reactors and expecting has 50 g/l final
Al2O3The aluminum oxide suspension of concentration, the target progression rates of the first settling step are 10%, it is necessary in settling step a）During supply
Answer the 10% of total aluminum oxide.Alumina precursor is the Al that concentration is 155 g/l2O3Sodium aluminate and concentration be 102 g/l
Al2O3Aluminum sulfate.The precipitation pH of first step is fixed on 9.5, and the precipitation pH of second step is fixed on 9.It is added in reactor
Water be 620 milliliters.
The first settling step a for operating 8 minutes at 30 DEG C）, the flow of aluminum sulfate is necessary for 2.1 ml/mins,
The flow of sodium aluminate is 2.6 ml/mins.Therefore sodium aluminate is 1.91 to the weight ratio of aluminum sulfate.
The second settling step for operating 30 minutes at 70 DEG C, the flow of aluminum sulfate is necessary for 5.2 ml/mins,
The flow of sodium aluminate is 6.3 ml/mins.Therefore sodium aluminate is 1.84 to the weight ratio of aluminum sulfate.
Preferably, second settling step is in 40 to 80 DEG C, preferably 45 to 70 DEG C and highly preferred 50 to 70 DEG C of temperature
It is lower to carry out.
Preferably, second settling step is carried out 5 to 45 minutes, preferably 7 to 40 minutes.
Second settling step is commonly used for obtaining with 20 to 100 g/l, preferably 20 to 80 g/l and more excellent
Select 20 to 50 g/l of Al2O3The aluminum oxide suspension of concentration.
Step d）：Filtering
The alumina preparation method of the present invention also includes the second settling step c of filtering）At the end of obtain suspension the step of.Institute
Filtration step is stated to carry out using method known to those skilled in the art.
Low point of the alumina gel that the filter capacity of the suspension obtained at the end of two settling steps passes through acquisition
Scattered property improves, it means that can improve the productivity ratio of the method for the present invention, and can also be expanded to commercial scale
Process.
The filtration step is advantageously followed by least one and preferably uses the washing step of water, and is preferably followed by one to three
Washing step, water is equal to the amount of the sediment of filtering.
First settling step a）, heating stepses b）With the second settling step c）And filtration step d）Series connection can be used for obtain
Must have less than 15%, preferably 5% to 15% and more preferably 6% to 14%, highly preferred 7% to 13% and even more preferably 7% to 10%
Dispersion rate, and 1 to 35 nanometer, preferably 2 to 35 nanometers of crystallite dimension specific alumina gel.
The alumina gel of acquisition additionally advantageously passes through X with 0.001% to 2 weight %, preferably 0.01% to 0.2 weight %
The sulfur content that ray fluorescence is measured, and 0.001% to 2 weight %, preferably 0.01% to 0.1 weight % pass through ICP-MS or inductance coupling
The sodium content that ICP-MS is measured is closed, the percentage by weight is represented relative to the gross mass of alumina gel.
Especially, the alumina gel or boehmite of powder type of the invention are made up of crystal grain, and it is in crystallographic direction
[020] size obtained using X-ray diffraction by application Scherrer formula and on [120] be respectively 2 to 20 nanometers and 2 to
35 nanometers.
Preferably, alumina gel of the invention has 1 to 15 nanometer of the crystallite dimension on crystallographic direction [020]
With 1 to 35 nanometer of the crystallite dimension on crystallographic direction [120].
The X-ray diffraction of alumina gel or boehmite is carried out using conventional powders method using diffractometer.
Scherrer formula are the formula used in the X-ray diffraction on powder or Polycrystalline, and it is by diffraction maximum
Width at intermediate altitude links together with crystallite dimension.It is described in detail in below with reference in works：Appl. Cryst.
(1978). 11, 102-113, Scherrer after sixty years: A survey and some new
Results in the determination of crystallite size, J.I. Langford and A.J.C.
Wilson。
Thus the low dispersiveness of the gel prepared can be used for promoting to use any method well known by persons skilled in the art, special
It is not to make the gel shaped step by mixing-extrusion, granulation and by oil dropping technique.
Step e）：Dry
According to the present invention, the second settling step c）And subsequent filtration step d）At the end of the alumina gel that obtains in drying
Step e）Middle drying is to obtain powder, and the drying steps at a temperature of 20 DEG C to 200 DEG C for example by drying 8 hours to 15
Hour is carried out by spray drying or by any other dry technology well known by persons skilled in the art.
The drying steps e is carried out by being spray-dried wherein）In the case of, by the second settling step and then
Filtration step at the end of the filter cake that obtains be absorbed in suspension.The suspension is then vertical what is contacted with stream of hot air
Fine drop is atomized into cylindrical chamber to evaporate water according to well known to a person skilled in the art principle.The powder quilt of acquisition
Hot-fluid is entrained in the cyclone separator or sleeve type filter for separating air with powder.
Preferably, the drying steps e is carried out by being spray-dried wherein）In the case of, according to Asep Bayu
Dani Nandiyanto, Kikuo Okuyama publication, Advanced Powder Technology, 22,1-19,
Operation scheme described in 2011 carries out the spray drying.
Step f）：Shaping
According to the present invention, in drying steps e）At the end of the powder that obtains in step f）It is middle to shape to obtain green material.
Term " green material " refers to the moulding material without heat treatment step.
The forming step f）It is preferred that entering by mixing-extrusion, by granulation, by oil dropping technique or by pelleting
OK.
Highly preferable, the forming step f）By mixing-extruding progress.
Step g）：Heat treatment
According to the present invention, in forming step f）At the end of the green material that obtains be then subjected to presence or absence of containing highest
In the case of the air stream of 60 volume % water, the step g of 2 to 10 hours is heat-treated at a temperature of 500 DEG C to 1000 DEG C）.
Preferably, the heat treatment step g）Operated at a temperature of 540 DEG C to 900 DEG C.
Preferably, the heat treatment step g）Operation 2 hours to 10 hours.
The heat treatment step g）Available for by boehmite conversion be final aluminum oxide.
The heat treatment step can be connected at a temperature of 50 DEG C to 120 DEG C using familiar to the person skilled in the art any in the past
The drying steps of technology.
The characteristic of the amorphous mesoporous aluminas of acquisition
The preparation method of the present invention can be used for obtaining the amorphous mesoporous aluminas with high intermediate value median pore diameter, the intermediate value mesopore
Diameter determined by distribution of pores figure by volume by mercury injection apparatus, its be advantageously 16 nanometers or bigger, preferably 18 nanometers or
Bigger, highly preferred 20 nanometers or bigger, even more preferably from 21 to 23 nanometers（Including limit value）.
Mesoporous aluminas prepared according to the methods of the invention does not contain micropore advantageously.Confirmed not by nitrogen porosimetry
There is micropore.
The mesoporous aluminas of the present invention advantageously has 0.50 ml/g or bigger, preferably 0.7 ml/g or bigger
The mesopore volume measured by mercury injection apparatus, i.e., included in a diameter of 2 to 50 nanometers（Including limit value）Hole in volume.
The total pore size volume measured by mercury injection method is be advantageously greater than 0.75 ml/g.
The mesoporous aluminas of the present invention generally comprise the total pore size volume that is determined by mercury injection method be less than 10%, it is preferably small
In 5% macropore ratio, the macropore is defined as the hole that diameter is more than 50 nanometers.
The mesoporous aluminas of the present invention, which generally has, is more than 100 m2/ g specific surface area.
The present invention will be illustrated in the examples below that now, the embodiment is not limited in any way in itself
System.
Embodiment
Embodiment 1（According to the present invention）：
Three kinds of aluminum oxide of the present invention are manufactured in the conventional equipment with 5 liters of reactors with 3 steps.
The concentration of precursor is as follows：Aluminum sulfate Al2(SO4) it is 102 g/l of Al2O3, sodium aluminate NaAlOO is 155 g/l
Al2O3。
The aluminum oxide of the present invention is manufactured using the following steps（A）：
a）Aluminum sulfate Al2(SO4)3It is co-precipitated with sodium aluminate NaAlOO under 30 DEG C and pH=9.1 through the first of 8 minutes：Be in progress shape
State is 8%.The state of progress corresponds to the ratio of the aluminum oxide formed during first step, i.e., 45 g/l of aluminum oxide is most
Final concentration.If using 5 liters of reactors and being expected 4 liters with 45 g/l of Al2O3Ultimate density aluminum oxide suspension, its
In the first settling step target state of progress be 8%, in settling step a）During the 8% of total aluminum oxide must be provided.First
The pH of the precipitation of step is fixed on 9.1, and the pH of the precipitation of second step is 9.1.It is initially present in the water in reactor
For 1330 milliliters.
The first settling step a for operating 8 minutes at 30 DEG C）, sulfuric acid aluminum flux is necessary for 6.1 ml/mins, sodium aluminate
Flow is 7.6 ml/mins, and water-carrying capacity is 69.7 ml/mins.Sodium aluminate is than thus to the weight of aluminum sulfate
1.91。
b）Heating through 20 to 30 minutes from 30 DEG C to 70 DEG C；
c）Aluminum sulfate Al2(SO4)3It is co-precipitated with sodium aluminate NaAlOO under 70 DEG C and pH=9.1 through the second of 30 minutes, be in progress shape
State is 92%；The second settling step for operating 30 minutes at 70 DEG C, sulfuric acid aluminum flux is necessary for 19 ml/mins, aluminic acid
Sodium flow is 23 ml/mins, and water-carrying capacity is 24.7 ml/mins.Sodium aluminate is than thus to the weight of aluminum sulfate
1.84。
d）Washed 3 times at 70 DEG C by the filtering of the displacement on P4 Buchner type sintering equipments, and with 5 liters of distilled water.
e）Dried whole night at 120 DEG C.
f）Shape green material.
Dry alumina gel is introduced into Brabender type mixers.While being mixed with 20 rpm, through 10 points
Clock addition be acidified to nitric acid be expressed as by the weight relative to the xerogel quality for introducing the mixer 3% total acid concentration
Water.Acid mixing continues 5 minutes.Neutralization procedure then is carried out by being added into mixer containing ammonia solution, by relative to acidifying
It is 200% that the percentage that the weight of the ammonia of the nitric acid amount of introducing mixer is represented in step, which is neutralized,.Mixing continues 3 minutes.
The thickener of acquisition is then extruded via 2 millimeters of trilobal die heads.
g）Heat treatment：The extrudate of acquisition is dried whole night, then at 800 DEG C in moist airflow at 100 DEG C
（The L/h/g of HSV=1, the water containing 30 volume %）Calcined 2 hours in tube furnace.
The distribution of pores of the aluminum oxide of acquisition is by using standard ASTM D 4284-83 under the maximum pressure of 4000 bars
Characterized using the mercury injection apparatus of the surface tension of 484 dynes per centimeters and 140 ° of contact angle.
Confirm that micropore is not present by nitrogen porosimetry.
The second aluminum oxide of the present invention is manufactured using the following steps（B）With the alchlor of the present invention（C）（Only it is heat-treated
Step g) is different）：
a）Aluminum sulfate Al2(SO4)3It is co-precipitated with sodium aluminate NaAlOO under 30 DEG C and pH=9.1 through the first of 8 minutes：Be in progress shape
State is 10%.The state of progress corresponds to the ratio of the aluminum oxide formed during first step, i.e., 45 g/l of aluminum oxide
Ultimate density.If using 5 liters of reactors and being expected 4 liters with 45 g/l of Al2O3Ultimate density aluminum oxide suspension,
The target state of progress of wherein the first settling step is 10%, in settling step a）During the 10% of total aluminum oxide must be provided.
The pH of the precipitation of first step is fixed on 9.1, and the pH of the precipitation of second step is 9.1.It is initially present in reactor
Water is 1330 milliliters.
The first settling step a for operating 8 minutes at 30 DEG C）, sulfuric acid aluminum flux is necessary for 7.6 ml/mins, sodium aluminate
Flow is 9.1 ml/mins, and water-carrying capacity is 24.6 ml/mins.Sodium aluminate is than thus to the weight of aluminum sulfate
1.91。
b）Heating through 20 to 30 minutes from 30 DEG C to 70 DEG C；
c）Aluminum sulfate Al2(SO4)3It is co-precipitated with sodium aluminate NaAlOO under 70 DEG C and pH=9.1 through the second of 30 minutes, be in progress shape
State is 90%；The second settling step for operating 30 minutes at 70 DEG C, sulfuric acid aluminum flux is necessary for 18.5 ml/mins, aluminium
Sour sodium flow is 29 ml/mins, and water-carrying capacity is 33.8 ml/mins.Sodium aluminate is than thus to the weight of aluminum sulfate
1.84。
d）Washed 3 times at 70 DEG C by the filtering of the displacement on P4 Buchner type sintering equipments, and with 5 liters of distilled water.
e）Dried whole night at 120 DEG C.
f）Shape green material.
Dry alumina gel is introduced into Brabender type mixers.While being mixed with 20 rpm, through 10 points
Clock addition be acidified to nitric acid be expressed as by the weight relative to the xerogel quality for introducing the mixer 3% total acid concentration
Water.Acid mixing continues 5 minutes.Neutralization procedure then is carried out by being added into mixer containing ammonia solution, by relative to acidifying
It is 200% that the percentage that the weight of the ammonia of the nitric acid amount of introducing mixer is represented in step, which is neutralized,.Mixing continues 3 minutes.
The thickener of acquisition is then extruded via 2 millimeters of trilobal die heads.
g）Heat treatment：The extrudate of acquisition is dried whole night, then at 800 DEG C in moist airflow at 100 DEG C
（The L/h/g of HSV=1, does not contain water to aluminum oxide B, 30 volume % water is contained to aluminum oxide C）Calcining 2 is small in tube furnace
When.
Table 1：The texture characteristic of the aluminum oxide of acquisition
To the first settling step selection development state be 5% to 13%, preferably 7% to 11% mean to obtain have it is as follows
The aluminum oxide of characteristic：High mesopore volume（More than 0.75 ml/g）, high-specific surface area（More than 75 m2/ g BET surface area）、
In the absence of micropore：Diameter is less than 1% less than what 10 nanometers of hole accounted for total pore size volume, in the hole that size is 10 to 50 nanometers
Upper preferred middle pore size distribution, most of hole is included in a diameter of 20 to 50 nanometers of hole（36%）, and high intermediate value mesopore
Diameter（16,21.3 and 22.5 nanometers）.
Embodiment 2（Contrast）：
Two kinds of alumina gels are synthesized according to identical scheme described in embodiment 1, but in the way of not meeting the present invention
Change the state of progress of the first settling step：0.20% to 35%.
Thus, the alumina amount provided during the first settling step is only provided.Step d）、e）And f）With embodiment 1
Described in those are identical.
In the case that the state of progress of the first settling step is 0% wherein, do not provided into first step containing before aluminium
Body.
This is deposited in 5 liters of reactors is carried out at 70 DEG C of temperature and 10.2 pH.
The concentration of aluminum precursor used is as follows：Al2(SO4The Al of)=102 g/l2O3, NaAlOO=155 g/l
Al2O3.It is carried out continuously the addition of reactant（Basic aluminium salt [AlOONa] and acid aluminium salt [Al2(SO4)3]）30 minutes, pH is adjusted
Save to 9.0.All precursors are contacted at a temperature of 70 DEG C.The final alumina concentration of target is 45 g/l.It is initially present in this anti-
It is 2000 milliliters to answer the water in device.The flow of aluminum sulfate is necessary for 20.6 ml/mins, and sodium aluminate flow is 25 ml/mins
Clock, and water-carrying capacity is 21 ml/mins.Sodium aluminate is to the weight of aluminum sulfate than being thus 1.84.
The suspension of acquisition then replaces to filter by the water on Buchner type sintering equipments, the aluminum oxide of acquisition
Gel distills water washing 3 times with 5 liters.
There is no sticky paste material.It is thus impossible to make it be configured to extrudate.
In the case that the state of progress of the first settling step is 20% wherein, aluminum oxide is then prepared as follows：
If using 5 liters of reactors and being expected 4 liters with 45 g/l of final Al2O3The aluminum oxide suspension of concentration, wherein the
The target state of progress of one settling step is 20%, in settling step a）During the 20% of total aluminum oxide must be provided.The first step
The pH of rapid precipitation is fixed on 9.5, and the pH of the precipitation of second step is 9.0.The water being initially present in reactor is
1330 milliliters.
The first settling step a for operating 8 minutes at 30 DEG C）, sulfuric acid aluminum flux is necessary for 15.2 ml/mins,
Sodium aluminate flow is 19 ml/mins, and water-carrying capacity is 49.2 ml/mins.Sodium aluminate to the weight ratio of aluminum sulfate thus
For 1.91.
The second settling step for operating 30 minutes at 70 DEG C, sulfuric acid aluminum flux is necessary for 16.5 ml/mins, aluminium
Sour sodium flow is 20 ml/mins, and water-carrying capacity is 30.1 ml/mins.Sodium aluminate is than thus to the weight of aluminum sulfate
1.84。
Shape green material：
Dry alumina gel is introduced into Brabender type mixers.While being mixed with 20 rpm, added through 10 minutes
Plus the water for total acid concentration that 3% is expressed as by the weight relative to the xerogel quality for introducing the mixer is acidified to nitric acid.Acid
Mixing continues 5 minutes.Neutralization procedure then is carried out by being added into mixer containing ammonia solution, by relative in acidification step
It is 200% that the percentage that the weight of the ammonia of the nitric acid amount of introducing mixer is represented, which is neutralized,.Mixing continues 3 minutes.
The thickener of acquisition is then extruded via 2 millimeters of trilobal die heads.
g）Heat treatment：The extrudate of acquisition is dried whole night, then at 800 DEG C in moist airflow at 100 DEG C
（The L/h/g of HSV=1, the water containing 30 volume %）Calcined 2 hours in tube furnace.
The distribution of pores of the aluminum oxide of acquisition is by using standard ASTM D 4284-83 under the maximum pressure of 4000 bars
Characterized using the mercury injection apparatus of the surface tension of 484 dynes per centimeters and 140 ° of contact angle.
Confirm that micropore is not present by nitrogen porosimetry.
In the case that the state of progress of settling step is 35% wherein, aluminum oxide is prepared as follows：
If using 5 liters of reactors and being expected 4 liters with 45 g/l of final Al2O3The aluminum oxide suspension of concentration, wherein the
The target state of progress of one settling step is 35%, in settling step a）During the 35% of total aluminum oxide must be provided.The first step
The pH of rapid precipitation is fixed on 9.5, and the pH of the precipitation of second step is 9.0.The water being initially present in reactor is
1330 milliliters.
The first settling step a for operating 8 minutes at 30 DEG C）, sulfuric acid aluminum flux is necessary for 22.7 ml/mins,
Sodium aluminate flow is 28.5 ml/mins, and water-carrying capacity is 32.2 ml/mins.Sodium aluminate to the weight ratio of aluminum sulfate by
This is 1.91.
The second settling step for operating 30 minutes at 70 DEG C, sulfuric acid aluminum flux is necessary for 14.4 ml/mins, aluminium
Sour sodium flow is necessary for 17.5 ml/mins, and water-carrying capacity is 34.7 ml/mins.Weight ratio of the sodium aluminate to aluminum sulfate
Thus it is 1.84.
Shape green material：
Dry alumina gel is introduced into Brabender type mixers.While being mixed with 20 rpm, added through 10 minutes
Plus the water for total acid concentration that 3% is expressed as by the weight relative to the xerogel quality for introducing the mixer is acidified to nitric acid.Acid
Mixing continues 5 minutes.Neutralization procedure then is carried out by being added into mixer containing ammonia solution, by relative in acidification step
It is 200% that the percentage that the weight of the ammonia of the nitric acid amount of introducing mixer is represented, which is neutralized,.Mixing continues 3 minutes.
The thickener of acquisition is then extruded via 2 millimeters of trilobal die heads.
Heat treatment：The extrudate of acquisition is dried whole night, then at 800 DEG C in moist airflow at 100 DEG C（HSV
=1 L/h/g, the water containing 30 volume %）Calcined 2 hours in tube furnace.
The distribution of pores of the aluminum oxide of acquisition is by using standard ASTM D 4284-83 under the maximum pressure of 4000 bars
Characterized using the mercury injection apparatus of the surface tension of 484 dynes per centimeters and 140 ° of contact angle.
Confirm that micropore is not present by nitrogen porosimetry.
Table 2：The texture characteristic of the aluminum oxide of embodiment 2
The embodiment shows, the aluminum oxide with expected hole property can not be obtained in single settling step（The first step
Rapid state of progress=0, aluminum oxide D）.
On the contrary, being resulted in the case of the method with two settling steps with high mesopore volume, high-ratio surface
The aluminum oxide of product and limited macropore volume.But, there is a high proportion of size to be less than 10 nanometers by the aluminum oxide E and F of acquisition
Hole, and 14.3 and 13.7 nanometers of corresponding intermediate value median pore diameter, therefore this do not meet the present invention.Therefore, the oxidation of acquisition
Aluminium E and F have the state of progress for the first step for not meeting the present invention, thus without being 10 to 50 nanometers of hole to size
Preferred unimodal middle pore size distribution, and 16 nanometers or bigger of intermediate value median pore diameter.
Claims (13)
1. preparing the method for amorphous mesoporous aluminas, methods described includes at least following steps：
a）It is at least one selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide for being precipitated in aqueous reaction medium
Alkaline precursor and it is at least one selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, the acidic precursor of hydrochloric acid and nitric acid first
Step, wherein at least one of the alkalescence or acidic precursor include aluminium, selects the relative stream of the acid and alkaline precursor
The pH for the reaction medium for measuring to obtain 8.5 to 10.5, and adjust the acid and one or more alkali of the one or more containing aluminium
The flow of property precursor is to obtain the state of progress of 5% to 13% first step, and the state of progress is defined as described first
Formed during settling step with Al2O3When the aluminum oxide of gauge is relative to the step c in preparation method）At the end of the oxygen that is formed
Change the ratio of aluminium total amount, the step is operated at a temperature of 20 DEG C to 90 DEG C and carried out 2 minutes to 30 minutes；
b）The step of suspension is heated to 40 DEG C to 90 DEG C of temperature 7 minutes to 45 minutes；
c）It is at least one selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide by being added into the suspension
Alkaline precursor and at least one acidic precursor selected from aluminum sulfate, aluminium chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid add to precipitate
Hot step b）At the end of the second step of suspension that obtains, wherein at least one of the alkalescence or acidic precursor are included
Aluminium, selects the relative discharge of the acid and alkaline precursor to contain to obtain the pH of 8.5 to 10.5 reaction medium, and to adjust
The flow of the acidity of aluminium and alkaline precursor is to obtain the state of progress of 87% to 95% second step, and the state of progress is defined
To be formed during second settling step with Al2O3When the aluminum oxide of gauge is relative to the step c in preparation method）Knot
The ratio of the aluminum oxide total amount formed during beam, the step is operated at a temperature of 40 DEG C to 90 DEG C and carried out 2 minutes to 50 points
Clock；
d）Filter the second settling step c）At the end of the suspension that obtains to obtain alumina gel the step of；
e）Drying steps d）The step of alumina gel of middle acquisition is to obtain powder；
f）Make step e）At the end of the powder forming that obtains to obtain green material the step of；
g）In the case of presence or absence of the air stream of the water containing most 60 volume %, in 500 DEG C to 1000 DEG C of temperature
Lower heat treatment step f）At the end of obtain green material the step of.
2. the method as described in claim 1, wherein the first settling step a）State of progress be 6% to 12%.
3. the method as described in claim 1 or claim 2, wherein the first settling step a）State of progress be 7% to 11%.
4. the method as described in any one of claims 1 to 3, wherein the alkaline precursor is sodium aluminate.
5. the method as described in any one of Claims 1-4, wherein the acidic precursor is aluminum sulfate.
6. the method as described in any one of claim 1 to 5, wherein in first settling step, the aqueous reaction is situated between
Matter is water, and the step is operated in the case of in the absence of organic additive under agitation.
7. amorphous mesoporous aluminas, its have 16 nanometers or the bigger intermediate value mesopore by volume determined by mercury injection apparatus it is straight
Footpath, 0.5 ml/g or the bigger mesopore volume measured by mercury injection apparatus, and pass through mercury injection method more than 0.75 ml/g
The total pore size volume measured.
8. amorphous mesoporous aluminas as claimed in claim 7, wherein macropore volume are less than the 10% of the total pore size volume.
9. amorphous mesoporous aluminas as claimed in claim 8, wherein macropore volume are less than the 5% of the total pore size volume.
10. the amorphous mesoporous aluminas as described in any one of claim 7 to 9, it does not have micropore.
11. the amorphous mesoporous aluminas as described in any one of claim 7 to 10, it has passes through mercury injection apparatus more than 18 nanometers
The intermediate value median pore diameter by volume determined.
12. amorphous mesoporous aluminas as claimed in claim 11, it has passes through pressing that mercury injection apparatus is determined more than 20 nanometers
The intermediate value median pore diameter of stereometer.
13. the amorphous mesoporous aluminas that can be obtained by the preparation method as described in any one of claim 1 to 6.
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| PCT/EP2015/062825 WO2015189199A1 (en) | 2014-06-13 | 2015-06-09 | Amorphous mesoporous alumina with optimised pore distribution and method for preparing same |
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| CN109956741B (en) * | 2019-03-11 | 2021-06-08 | 山东天汇研磨耐磨技术开发有限公司 | Microcrystalline ceramic corundum abrasive and manufacturing method thereof |
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| FR3022237A1 (en) | 2015-12-18 |
| US20170101324A1 (en) | 2017-04-13 |
| JP2017523109A (en) | 2017-08-17 |
| WO2015189199A1 (en) | 2015-12-17 |
| FR3022237B1 (en) | 2017-09-01 |
| EP3154907A1 (en) | 2017-04-19 |
| DK3154907T3 (en) | 2019-06-24 |
| CN107155324B (en) | 2021-05-25 |
| EP3154907B1 (en) | 2019-04-03 |
| JP6623181B2 (en) | 2019-12-18 |
| US10131547B2 (en) | 2018-11-20 |
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